Photolithographic methods

ABSTRACT

Methods of forming an electronic device, comprising in sequence: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) forming a photoresist layer over the one or more layers to be patterned, wherein the photoresist layer is formed from a composition that comprises: a matrix polymer comprising a unit having an acid labile group; a photoacid generator; and an organic solvent; (c) coating a photoresist overcoat composition over the photoresist layer, wherein the overcoat composition comprises a quenching polymer and an organic solvent, wherein the quenching polymer comprises a unit having a basic moiety effective to neutralize acid generated by the photoacid generator in a surface region of photoresist layer; (d) exposing the photoresist layer to activating radiation; (e) heating the substrate in a post-exposure bake process; and (f) developing the exposed film with an organic solvent developer. The methods have particular applicability in the semiconductor manufacturing industry.

This application claims the benefit of priority under 35 U.S.C. §119(e)to U.S. Provisional Application No. 61/922,784, filed Dec. 31, 2013, theentire contents of which are incorporated herein by reference.

BACKGROUND

The invention relates generally to the manufacture of electronicdevices. More specifically, this invention relates to photolithographicmethods and photoresist overcoat compositions which allow for theformation of fine patterns using a negative tone development process.

In the semiconductor manufacturing industry, photoresist materials areused for transferring an image to one or more underlying layers, such asmetal, semiconductor and dielectric layers, disposed on a semiconductorsubstrate, as well as to the substrate itself. To increase theintegration density of semiconductor devices and allow for the formationof structures having dimensions in the nanometer range, photoresists andphotolithography processing tools having high-resolution capabilitieshave been and continue to be developed.

Positive-tone chemically amplified photoresists are conventionally usedfor high-resolution processing. Such resists typically employ a resinhaving acid-labile leaving groups and a photoacid generator. Exposure toactinic radiation causes the acid generator to form an acid which,during post-exposure baking, causes cleavage of the acid-labile groupsin the resin. This creates a difference in solubility characteristicsbetween exposed and unexposed regions of the resist in an aqueousalkaline developer solution. Exposed regions of the resist are solublein the aqueous alkaline developer and are removed from the substratesurface, whereas unexposed regions, which are insoluble in thedeveloper, remain after development to form a positive image.

One approach to achieving nm-scale feature sizes in semiconductordevices is the use of short wavelengths of light, for example, 193 nm orless, during exposure of chemically amplified photoresists. To furtherimprove lithographic performance, immersion lithography tools have beendeveloped to effectively increase the numerical aperture (NA) of thelens of the imaging device, for example, a scanner having a KrF or ArFlight source. This is accomplished by use of a relatively highrefractive index fluid (i.e., an immersion fluid) between the lastsurface of the imaging device and the upper surface of the semiconductorwafer. The immersion fluid allows a greater amount of light to befocused into the resist layer than would occur with an air or inert gasmedium. When using water as the immersion fluid, the maximum numericalaperture can be increased, for example, from 1.2 to 1.35. With such anincrease in numerical aperture, it is possible to achieve a 40 nmhalf-pitch resolution in a single exposure process, thus allowing forimproved design shrink. This standard immersion lithography process,however, is generally not suitable for manufacture of devices requiringgreater resolution, for example, for the 32 nm and 22 nm half-pitchnodes.

Considerable effort has been made to extend the practical resolutionbeyond that achieved with positive tone development from both amaterials and processing standpoint. One such example involves negativetone development (NTD) of a traditionally positive-type chemicallyamplified photoresist. The NTD process allows for improved resolutionand process window as compared with standard positive tone imaging bymaking use of the superior imaging quality obtained with bright fieldmasks for printing critical dark field layers. NTD resists typicallyemploy a resin having acid-labile (acid-cleavable) groups and aphotoacid generator. Exposure to actinic radiation causes the photoacidgenerator to form an acid which, during post-exposure baking, causescleavage of the acid-labile groups giving rise to a polarity switch inthe exposed regions. As a result, a difference in solubilitycharacteristics is created between exposed and unexposed regions of theresist such that unexposed regions of the resist can be removed byorganic developers such as ketones, esters or ethers, leaving behind apattern created by the insoluble exposed regions.

Problems in NTD processes in the form of necking of contact holes andT-topping of line and trench patterns in the developed resist patternsare described in U.S. Application Pub. No. US2013/0244438A1. Suchproblems are possibly caused by diffusion of stray light beneath edgesof the photomask opaque pattern, undesirably causing polarity-switchingin those “dark” regions at the resist surface. In an effort to addressthis problem, the '438 publication discloses use of a photoresistovercoat that includes a basic quencher, a polymer and an organicsolvent. The basic quenchers described in the '438 publication are ofthe additive type.

The inventors have discovered that the use of an additive-type basisquencher in the NTD process suffers from various problems. Theseproblems include, for example, undesired diffusion of additive basicquenchers into the underlying photoresist and/or overcoat polymers,which can renders the effective amount of the basic quencherunpredictable. In addition, when used in an immersion lithographyprocess, additive-type basic quenchers can leach into the immersionfluid and cause fouling of the immersion scanner optics.

There is a continuing need in the art for improved photolithographicmethods and compositions for negative tone development which allow forthe formation of fine patterns in electronic device fabrication andwhich avoid or conspicuously ameliorate one or more of the foregoingproblems associated with the state of the art.

SUMMARY OF THE INVENTION

In accordance with an aspect of the invention, methods of formingelectronic devices are provided. The methods comprise: A method offorming an electronic device, comprising in sequence: (a) providing asemiconductor substrate comprising one or more layers to be patterned;(b) forming a photoresist layer over the one or more layers to bepatterned, wherein the photoresist layer is formed from a compositionthat comprises: a matrix polymer comprising a unit having an acid labilegroup; a photoacid generator; and an organic solvent; (c) coating aphotoresist overcoat composition over the photoresist layer, wherein theovercoat composition comprises a quenching polymer and an organicsolvent, wherein the quenching polymer comprises a unit having a basicmoiety effective to neutralize acid generated by the photoacid generatorin a surface region of photoresist layer; (d) exposing the photoresistlayer to activating radiation; (e) heating the substrate in apost-exposure bake process; and (f) developing the exposed film with anorganic solvent developer.

As used herein: “mol %” means mole percent based on the polymer, unlessotherwise specified, and numbers shown with polymer units are in mol %unless otherwise specified; “Mw” means weight average molecular weight;“Mn” means number average molecular weight; “PDI” means polydispersityindex=Mw/Mn; “copolymer” is inclusive of polymers containing two or moredifferent types of polymerized units; “alkyl” and “alkylene” areinclusive of linear, branched and cyclic alkyl and alkylene structures,respectively, unless otherwise specified or indicated by context; andthe articles “a” and “an” are inclusive of one or more unless otherwiseindicated by context.

DESCRIPTION OF THE DRAWINGS

The present invention will be described with reference to the followingdrawings, in which like reference numerals denote like features, and inwhich:

FIGS. 1A-C illustrates a process flow for forming a photolithographicpattern by negative tone development in accordance with the invention.

DETAILED DESCRIPTION

Photoresist Overcoat Compositions

The photoresist overcoat compositions useful in the invention whencoated over a photoresist layer in a negative tone development processcan provide various benefits, such as one or more of geometricallyuniform resist patterns, reduced reflectivity during resist exposure,improved focus latitude, improved exposure latitude and reduceddefectivity. These benefits can be achieved when using the compositionsin dry lithography or immersion lithography processes. The exposurewavelength is not particularly limited except by the photoresistcompositions, with 248 nm or sub-200 nm such as 193 nm (immersion or drylithography) or an EUV wavelength (e.g., 13.4 nm) being typical. Whenused in immersion lithography, the overcoat compositions can be used toform an effective barrier layer for avoidance of leaching of photoresistcomponents into the immersion fluid and to provide desirable contactangle characteristics with the immersion fluid to allow for increasedexposure scan speeds.

The photoresist overcoat compositions include a quenching polymer, anorganic solvent and can include additional optional components. Whereused in an immersion lithography process, the quenching polymer canimpart to layers formed from the compositions beneficial barrierproperties to minimize or prevent migration of photoresist componentsinto an immersion fluid, and beneficial contact angle characteristics toprovide for a high immersion fluid receding contact angle at theovercoat/immersion fluid interface, thereby allowing for faster exposuretool scanning speeds. A layer of the overcoat composition in a driedstate typically has a water receding contact angle of from 70° to 85°,preferably from 75 to 80°. The phrase “in a dried state” meanscontaining 8 wt % or less of solvent, based on the entire composition.

The polymer should have very good developability before and afterphotolithographic treatment. To minimize residue defects originated fromthe overcoat materials, the dissolution rate of a dried layer of theovercoat composition should be greater than that of the underlyingphotoresist layer in the developer used in the patterning process. Thepolymer typically exhibits a developer dissolution rate of 100 Å/secondor higher, preferably 1000 Å/second or higher. The polymer is soluble inthe organic solvent of the overcoat composition, described herein, andis soluble in organic developers used in negative tone developmentprocesses.

Quenching polymers useful in the overcoat compositions can behomopolymers or can be copolymers having a plurality of distinct repeatunits, for example, two, three, four or more distinct repeat units. Thequenching polymer may include units having polymerizable groups chosen,for example, from one or more of (alkyl)acrylate, (alkyl)acrylamide,allyl, maleimide styrene, vinyl, polycyclic (e.g., norbornene) and othertypes of units. The quenching polymer can be a random polymer, a blockpolymer, or a gradient copolymer having a graded change in compositionfrom one monomer unit-type to another monomer unit-type along the lengthof the polymer chain.

The quenching polymer includes a unit which is formed from a monomerhaving a basic moiety. This unit is present for purposes of neutralizingacid in the regions of an underlying photoresist layer intended to beunexposed (dark region), which acid is generated by stray light in thesurface region of the photoresist layer. This is believed to allow forimprovement in depth of focus in the defocus area and exposure latitudeby controlling unwanted deprotection reaction in the unexposed areas. Asa result, irregularities in the profile, for example, necking andT-topping, in formed resist patterns can be minimized or avoided.

The basic moiety-containing unit is preferably formed from a monomerchosen from one or more of: monomers whose polymerizable unit is chosenfrom (alkyl)acrylate, vinyl, allyl and maleimide, and whose basic moietyis a nitrogen-containing group chosen from: amines such as amino ethers,pyridines, anilines, indazoles, pyrroles, pyrazoles, pyrazines,guanidiniums and imines; amides such as carbamates, pyrrolidinones,maleimides, imidazoles and imides; and derivates thereof. Of these,(alkyl)acrylate polymerizable groups and amine-containing basic moietiesare preferred.

The pKa (in water) of the basic moiety-containing monomer is preferablyfrom 5 to 50, more preferably from 8 to 40 and most preferably from 10to 35. The pKa value of the basic moiety-containing monomer and thequenching polymer as a whole will typically have the same orsubstantially the same value.

Exemplary suitable monomers for use in forming a basic moiety-containingunit of the quenching polymer include the following:

Of these basic moiety-containing monomers, the following are preferred:

The content of the basic moiety-containing unit(s) in the quenchingpolymer should be sufficient to substantially or completely eliminateacid-induced deprotection reaction in the dark regions of an underlyingphotoresist layer while allowing such reaction to occur in the brightregions (those regions intended to be exposed) of the layer. The desiredcontent of the basic moiety-containing unit(s) in the quenching polymerwill depend, for example, on the content of the photoacid generator inthe photoresist layer, and on the intended use of the overcoat, whetherin a dry or immersion lithography process. Typically the content of thebasic moiety-containing unit(s) in the quenching polymer for a drylithography process will be from 0.1 to 100 mole %, preferably from 1 to50 mole % and more preferably from 2 to 20 mole %, based on thequenching polymer. For an immersion lithography process, the content istypically from 0.1 to 30 mole %, preferably from 0.5 to 20 mole % andmore preferably from 2 to 15 mole %, based on the quenching polymer.

The polymer can optionally include one or more additional type of unit.For example, in the case of an immersion lithography process, it may bedesirable to include one or more unit which would allow the overcoatcomposition to function as an immersion topcoat, thereby preventingleaching of components from the underlying photoresist layer into theimmersion fluid.

For this purpose, the quenching polymer preferably includes a unitformed from a monomer having the following general formula (I):

wherein: R₁ is chosen from hydrogen and substituted or unsubstituted C1to C3 alkyl, preferably hydrogen or methyl; R₂ is chosen fromsubstituted and unsubstituted C1 to C15 alkyl, preferably C4 to C8alkyl, more preferably C4 to C6 alkyl, the substituted alkyls including,for example, haloalkyl and haloalcohol such as fluoroalkyl andfluoroalcohol, and is preferably branched to provide higher recedingcontact angles; X is oxygen, sulfur or is represented by the formulaNR₃, wherein R₃ is chosen from hydrogen and substituted andunsubstituted C1 to C10 alkyl, preferably C1 to C5 alkyl; and Z is asingle bond or a spacer unit chosen from substituted and unsubstitutedaliphatic (such as C1 to C6 alkylene) and aromatic hydrocarbons, andcombinations thereof, optionally with one or more linking moiety chosenfrom —O—, —S—, —COO— and —CONR₄— wherein R₄ is chosen from hydrogen andsubstituted and unsubstituted C1 to C10 alkyl, preferably C2 to C6,alkyl.

The monomer of general formula (I) is preferably of the followinggeneral formula (II):

wherein R₁ and Z are as defined above, and R₅, R₆, and R₇ independentlyrepresent hydrogen or a C₁ to C₃ alkyl, fluoroalkyl or fluoroalcoholgroup. Suitable monomers of general formula (II) are described among theabove-exemplified structures.

Exemplary suitable monomers of general formula (I) are described below,but are not limited to these structures. For purposes of thesestructures, “R₁” and “X” are as defined above.

When present in the quenching polymer for use in immersion lithography,this additional unit is typically present in the quenching polymer in anamount of from 70 to 99.9 mol %, preferably from 80 to 99.5 mol % andmore preferably from 85 to 98 mol %, based on the quenching polymer.

Exemplary quenching polymers useful in the photoresist compositionsinclude the following in mol %:

The overcoat compositions typically include a single polymer, but canoptionally include one or more additional quenching polymer as describedabove or other polymers. Suitable polymers and monomers for use in theovercoat compositions are commercially available and/or can readily bemade by persons skilled in the art.

The content of the quenching polymer may depend, for example, on whetherthe lithography is a dry or immersion-type process. For example, thequenching polymer lower limit for immersion lithography is generallydictated by the need to prevent leaching of components from theunderlying photoresist layer into the immersion fluid. The quenchingpolymer is typically present in the overcoat composition in an amount offrom 80 to 100 wt %, more typically from 90 to 100 wt %, 95 to 100 wt %,with 100 wt % being typical, based on total solids of the overcoatcomposition. The weight average molecular weight of the quenchingpolymer is typically less than 400,000, preferably from 2000 to 50,000,more preferably from 2000 to 25,000.

The overcoat compositions further include an organic solvent or mixtureof organic solvents. Suitable solvent materials to formulate and castthe overcoat composition exhibit excellent solubility characteristicswith respect to the non-solvent components of the overcoat composition,but do not appreciably dissolve an underlying photoresist layer.Suitable organic solvents for the overcoat composition include, forexample: alkyl esters such as alkyl propionates such as n-butylpropionate, n-pentyl propionate, n-hexyl propionate and n-heptylpropionate, and alkyl butyrates such as n-butyl butyrate, isobutylbutyrate and isobutyl isobutyrate; ketones such as2,5-dimethyl-4-hexanone and 2,6-dimethyl-4-heptanone; aliphatichydrocarbons such as n-heptane, n-nonane, n-octane, n-decane,2-methylheptane, 3-methylheptane, 3,3-dimethylhexane and2,3,4-trimethylpentane, and fluorinated aliphatic hydrocarbons such asperfluoroheptane; and alcohols such as straight, branched or cyclicC₄-C₉ monohydric alcohol such as 1-butanol, 2-butanol,3-methyl-1-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol,2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol,2-octanol, 3-hexanol, 3-heptanol, 3-octanol and 4-octanol;2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanoland 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, and C₅-C₉ fluorinateddiols such as 2,2,3,3,4,4-hexafluoro-1,5-pentanediol,2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol and2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol; and mixturescontaining one or more of these solvents. Of these organic solvents,alkyl propionates, alkyl butyrates and ketones, preferably branchedketones, are preferred and, more preferably, C₈-C₉ alkyl propionates,C₈-C₉ alkyl propionates, C₈-C₉ ketones, and mixtures containing one ormore of these solvents. Suitable mixed solvents include, for example,mixtures of an alkyl ketone and an alkyl propionate such as the alkylketones and alkyl propionates described above. The solvent component ofthe overcoat composition is typically present in an amount of from 90 to99 wt % based on the overcoat composition.

The photoresist overcoat compositions can include one or more optionalmaterials. For example, the compositions can include one or more ofactinic and contrast dyes, anti-striation agents, and the like. Ofthese, actinic and contrast dyes are preferred for enhancingantireflective properties of layers formed from the compositions. Suchoptional additives if used are typically present in the composition inminor amounts such as from 0.1 to 10 wt % based on total solids of theovercoat composition. The overcoat compositions are preferably free ofacid generator compounds, for example, thermal acid generator compoundsand photoacid generator compounds, as such compounds may neutralize theeffect of the basic quencher in the overcoat compositions.

The photoresist overcoat compositions can be prepared following knownprocedures. For example, the compositions can be prepared by dissolvingsolid components of the composition in the solvent components. Thedesired total solids content of the compositions will depend on factorssuch as the particular polymer(s) in the composition and desired finallayer thickness. Preferably, the solids content of the overcoatcompositions is from 1 to 10 wt %, more preferably from 1 to 5 wt %,based on the total weight of the composition.

Resist overcoat layers formed from the compositions typically have anindex of refraction of 1.4 or greater at 193 nm, preferably 1.47 orgreater at 193 nm. The index of refraction can be tuned by changing thecomposition of the polymer(s) or other components of the overcoatcomposition. For example, increasing the relative amount of organiccontent in the overcoat composition may provide increased refractiveindex of the layer. Preferred overcoat composition layers will have arefractive index between that of the immersion fluid and the photoresistat the target exposure wavelength.

Reflectivity of the overcoat layer can be reduced if the refractiveindex of the overcoat layer (n₁) is the geometric mean of that of thematerials on either side (n₁=√(n₀ n₂)), where n₀ is the refractive indexof water in the case of immersion lithography or air for drylithography, and n₂ is the refractive index of the photoresist. Also toenhance antireflective properties of layers formed from the overcoatcompositions, it is preferred that the thickness of the overcoat (d₁) ischosen such that the wavelength in the overcoat is one quarter thewavelength of the incoming wave (λ₀). For a quarter wavelengthantireflective coating of an overcoat composition with a refractiveindex n₁, the thickness d₁ that gives minimum reflection is calculatedby d₁=λ₀/(4n₁).

Photoresist Compositions

Photoresist compositions useful in the invention includechemically-amplified photoresist compositions comprising a matrixpolymer that is acid-sensitive, meaning that as part of a layer of thephotoresist composition, the polymer and composition layer undergo achange in solubility in an organic developer as a result of reactionwith acid generated by a photoacid generator following softbake,exposure to activating radiation and post exposure bake. The change insolubility is brought about when acid-labile groups such asphotoacid-labile ester or acetal groups in the matrix polymer undergo aphotoacid-promoted deprotection reaction on exposure to activatingradiation and heat treatment. Suitable photoresist compositions usefulfor the invention are commercially available

For imaging at sub-200 nm wavelengths such as 193 nm, the matrix polymeris typically substantially free (e.g., less than 15 mole %) of phenyl,benzyl or other aromatic groups where such groups are highly absorbingof the radiation. Suitable polymers that are substantially or completelyfree of aromatic groups are disclosed in European application EP930542A1and U.S. Pat. Nos. 6,692,888 and 6,680,159, all of the Shipley Company.Preferable acid labile groups include, for example, acetal groups orester groups that contain a tertiary non-cyclic alkyl carbon (e.g.,t-butyl) or a tertiary alicyclic carbon (e.g., methyladamantyl)covalently linked to a carboxyl oxygen of an ester of the matrixpolymer.

Suitable matrix polymers further include polymers that contain(alkyl)acrylate units, preferably including acid-labile (alkyl)acrylateunits, such as t-butyl acrylate, t-butyl methacrylate, methyladamantylacrylate, methyl adamantyl methacrylate, ethylfenchyl acrylate,ethylfenchyl methacrylate, and the like, and other non-cyclic alkyl andalicyclic (alkyl)acrylates. Such polymers have been described, forexample, in U.S. Pat. No. 6,057,083, European Published ApplicationsEP01008913A1 and EP00930542A1, and U.S. Pat. No. 6,136,501.

Other suitable matrix polymers include, for example, those which containpolymerized units of a non-aromatic cyclic olefin (endocyclic doublebond) such as an optionally substituted norbornene, for example,polymers described in U.S. Pat. Nos. 5,843,624 and 6,048,664.

Still other suitable matrix polymers include polymers that containpolymerized anhydride units, particularly polymerized maleic anhydrideand/or itaconic anhydride units, such as disclosed in European PublishedApplication EP01008913A1 and U.S. Pat. No. 6,048,662.

Also suitable as the matrix polymer is a resin that contains repeatunits that contain a hetero atom, particularly oxygen and/or sulfur (butother than an anhydride, i.e., the unit does not contain a keto ringatom). The heteroalicyclic unit can be fused to the polymer backbone,and can comprise a fused carbon alicyclic unit such as provided bypolymerization of a norbornene group and/or an anhydride unit such asprovided by polymerization of a maleic anhydride or itaconic anhydride.Such polymers are disclosed in PCT/US01/14914 and U.S. Pat. No.6,306,554. Other suitable hetero-atom group containing matrix polymersinclude polymers that contain polymerized carbocyclic aryl unitssubstituted with one or more hetero-atom (e.g., oxygen or sulfur)containing groups, for example, hydroxy naphthyl groups, such asdisclosed in U.S. Pat. No. 7,244,542.

Blends of two or more of the above-described matrix polymers cansuitably be used in the photoresist compositions.

Suitable matrix polymers for use in the photoresist compositions arecommercially available and can readily be made by persons skilled in theart. The matrix polymer is present in the resist composition in anamount sufficient to render an exposed coating layer of the resistdevelopable in a suitable developer solution. Typically, the matrixpolymer is present in the composition in an amount of from 50 to 95 wt %based on total solids of the resist composition. The weight averagemolecular weight M_(w), of the matrix polymer is typically less than100,000, for example, from 5000 to 100,000, more typically from 5000 to15,000.

The photoresist composition further comprises a photoactive componentsuch as a photoacid generator (PAG) employed in an amount sufficient togenerate a latent image in a coating layer of the composition uponexposure to activating radiation. For example, the photoacid generatorwill suitably be present in an amount of from about 1 to 20 wt % basedon total solids of the photoresist composition. Typically, lesseramounts of the PAG will be suitable for chemically amplified resists ascompared with non-chemically amplified materials.

Suitable PAGs are known in the art of chemically amplified photoresistsand include, for example: onium salts, for example, triphenylsulfoniumtrifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfoniumtrifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfoniumtrifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate;nitrobenzyl derivatives, for example, 2-nitrobenzyl-p-toluenesulfonate,2,6-dinitrobenzyl-p-toluenesulfonate, and2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, for example,1,2,3-tris(methanesulfonyloxy)benzene,1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, forexample, bis(benzenesulfonyl)diazomethane,bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example,bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, andbis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid esterderivatives of an N-hydroxyimide compound, for example,N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimidetrifluoromethanesulfonic acid ester; and halogen-containing triazinecompounds, for example,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One ormore of such PAGs can be used.

Suitable solvents for the photoresist compositions include, for example:glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycolmonomethyl ether, and propylene glycol monomethyl ether; propyleneglycol monomethyl ether acetate; lactates such as methyl lactate andethyl lactate; propionates such as methyl propionate, ethyl propionate,ethyl ethoxy propionate and methyl-2-hydroxy isobutyrate; Cellosolveesters such as methyl Cellosolve acetate; aromatic hydrocarbons such astoluene and xylene; and ketones such as acetone, methylethyl ketone,cyclohexanone and 2-heptanone. A blend of solvents such as a blend oftwo, three or more of the solvents described above also are suitable.The solvent is typically present in the composition in an amount of from90 to 99 wt %, more typically from 95 to 98 wt %, based on the totalweight of the photoresist composition.

The photoresist compositions can further include other optionalmaterials. For example, negative-acting resist compositions typicallyalso include a crosslinker component. Suitable crosslinker componentsinclude, for example, an amine-based material such as a melamine resin,that will cure, crosslink or harden upon exposure to acid on exposure ofa photoacid generator to activating radiation. Preferred crosslinkersinclude amine-based materials, including melamine, glycolurils,benzoguanamine-based materials and urea-based materials.Melamine-formaldehyde resins are generally most preferred. Suchcrosslinkers are commercially available, e.g. the melamine resins soldby American Cyanamid under the trade names Cymel 300, 301 and 303.Glycoluril resins are sold by American Cyanamid under trade names Cymel1170, 1171, 1172, urea-based resins are sold under the trade names ofBeetle 60, 65 and 80, and benzoguanamine resins are sold under the tradenames Cymel 1123 and 1125. For imaging at sub-200 nm wavelengths such as193 nm, preferred negative-acting photoresists are disclosed in WO03077029 to the Shipley Company.

The photoresist compositions can also include other optional materials.For example, the compositions can include one or more of actinic andcontrast dyes, anti-striation agents, plasticizers, speed enhancers,sensitizers, and the like. Such optional additives if used are typicallypresent in the composition in minor amounts such as from 0.1 to 10 wt %based on total solids of the photoresist composition.

A preferred optional additive of the resist compositions is an addedbase. Suitable bases are described above with respect to the basicquencher in the overcoat composition. The added base is suitably used inrelatively small amounts, for example, from 0.01 to 5 wt %, preferablyfrom 0.1 to 2 wt %, based on total solids of the photoresistcomposition.

The photoresists can be prepared following known procedures. Forexample, the resists can be prepared as coating compositions bydissolving the components of the photoresist in a suitable solvent, forexample, one or more of: a glycol ether such as 2-methoxyethyl ether(diglyme), ethylene glycol monomethyl ether, propylene glycol monomethylether; propylene glycol monomethyl ether acetate; lactates such as ethyllactate or methyl lactate, with ethyl lactate being preferred;propionates, particularly methyl propionate, ethyl propionate and ethylethoxy propionate; a Cellosolve ester such as methyl Cellosolve acetate;an aromatic hydrocarbon such toluene or xylene; or a ketone such asmethylethyl ketone, cyclohexanone and 2-heptanone. The desired totalsolids content of the photoresist will depend on factors such as theparticular polymers in the composition, final layer thickness andexposure wavelength. Typically the solids content of the photoresistvaries from 1 to 10 wt %, more typically from 2 to 5 wt %, based on thetotal weight of the photoresist composition.

Negative Tone Development Methods

Processes in accordance with the invention will now be described withreference to FIGS. 1A-C, which illustrates an exemplary process flow forforming a photolithographic pattern by negative tone development.

FIG. 1A depicts in cross-section a substrate 100 which may includevarious layers and features. The substrate can be of a material such asa semiconductor, such as silicon or a compound semiconductor (e.g.,III-V or II-VI), glass, quartz, ceramic, copper and the like. Typically,the substrate is a semiconductor wafer, such as single crystal siliconor compound semiconductor wafer, and may have one or more layers andpatterned features formed on a surface thereof. One or more layers to bepatterned 102 may be provided over the substrate 100. Optionally, theunderlying base substrate material itself may be patterned, for example,when it is desired to form trenches in the substrate material. In thecase of patterning the base substrate material itself, the pattern shallbe considered to be formed in a layer of the substrate.

The layers may include, for example, one or more conductive layers suchas layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten,alloys, nitrides or silicides of such metals, doped amorphous silicon ordoped polysilicon, one or more dielectric layers such as layers ofsilicon oxide, silicon nitride, silicon oxynitride, or metal oxides,semiconductor layers, such as single-crystal silicon, and combinationsthereof. The layers to be etched can be formed by various techniques,for example, chemical vapor deposition (CVD) such as plasma-enhancedCVD, low-pressure CVD or epitaxial growth, physical vapor deposition(PVD) such as sputtering or evaporation, or electroplating. Theparticular thickness of the one or more layers to be etched 102 willvary depending on the materials and particular devices being formed.

Depending on the particular layers to be etched, film thicknesses andphotolithographic materials and process to be used, it may be desired todispose over the layers 102 a hard mask layer and/or a bottomantireflective coating (BARC) over which a photoresist layer 104 is tobe coated. Use of a hard mask layer may be desired, for example, withvery thin resist layers, where the layers to be etched require asignificant etching depth, and/or where the particular etchant has poorresist selectivity. Where a hard mask layer is used, the resist patternsto be formed can be transferred to the hard mask layer which, in turn,can be used as a mask for etching the underlying layers 102. Suitablehard mask materials and formation methods are known in the art. Typicalmaterials include, for example, tungsten, titanium, titanium nitride,titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride,hafnium oxide, amorphous carbon, silicon oxynitride and silicon nitride.The hard mask layer can include a single layer or a plurality of layersof different materials. The hard mask layer can be formed, for example,by chemical or physical vapor deposition techniques.

A bottom antireflective coating may be desirable where the substrateand/or underlying layers would otherwise reflect a significant amount ofincident radiation during photoresist exposure such that the quality ofthe formed pattern would be adversely affected. Such coatings canimprove depth-of-focus, exposure latitude, linewidth uniformity and CDcontrol. Antireflective coatings are typically used where the resist isexposed to deep ultraviolet light (300 nm or less), for example, KrFexcimer laser light (248 nm) or ArF excimer laser light (193 nm). Theantireflective coating can comprise a single layer or a plurality ofdifferent layers. Suitable antireflective materials and methods offormation are known in the art. Antireflective materials arecommercially available, for example, those sold under the AR™ trademarkby Rohm and Haas Electronic Materials LLC (Marlborough, Mass. USA), suchas AR™40A and AR™124 antireflectant materials.

A photoresist layer 104 formed from a composition such as describedherein is disposed on the substrate over the antireflective layer (ifpresent). The photoresist composition can be applied to the substrate byspin-coating, dipping, roller-coating or other conventional coatingtechnique. Of these, spin-coating is typical. For spin-coating, thesolids content of the coating solution can be adjusted to provide adesired film thickness based upon the specific coating equipmentutilized, the viscosity of the solution, the speed of the coating tooland the amount of time allowed for spinning. A typical thickness for thephotoresist layer 104 is from about 500 to 3000 Å.

The photoresist layer can next be softbaked to minimize the solventcontent in the layer, thereby forming a tack-free coating and improvingadhesion of the layer to the substrate. The softbake can be conducted ona hotplate or in an oven, with a hotplate being typical. The softbaketemperature and time will depend, for example, on the particularmaterial of the photoresist and thickness. Typical softbakes areconducted at a temperature of from about 90 to 150° C., and a time offrom about 30 to 90 seconds.

A photoresist overcoat layer 106 formed from an overcoat composition asdescribed herein is formed over the photoresist layer 104. The overcoatcomposition is typically applied to the substrate by spin-coating. Thesolids content of the coating solution can be adjusted to provide adesired film thickness based upon the specific coating equipmentutilized, the viscosity of the solution, the speed of the coating tooland the amount of time allowed for spinning. To reduce reflectivity ofthe overcoat layer, the thickness is preferably chosen such that thewavelength in the overcoat is one quarter the wavelength of the incomingwave. A typical thickness for the photoresist overcoat layer 106 is from200 to 1000 Å.

The photoresist overcoat layer can next be baked to remove minimize thesolvent content in the layer. The bake can be conducted on a hotplate orin an oven, with a hotplate being typical. Typical bakes are conductedat a temperature of from about 80 to 120° C., and a time of from about30 to 90 seconds. The basic quencher may be present in the overcoatlayer 106 dispersed homogeneously through the overcoat layer, or may bepresent as a segregated or graded quencher region 107.

The photoresist layer 104 is next exposed to activating radiation 108through a first photomask 110 to create a difference in solubilitybetween exposed and unexposed regions. Reference herein to exposing aphotoresist composition to radiation that is activating for thecomposition indicates that the radiation is capable of forming a latentimage in the photoresist composition. The photomask has opticallytransparent and optically opaque regions 112, 114 corresponding toregions of the resist layer to remain and be removed, respectively, in asubsequent development step. The exposure wavelength is typicallysub-400 nm, sub-300 nm or sub-200 nm, with 248 nm and 193 nm beingtypical. The methods find use in immersion or dry (non-immersion)lithography techniques. The exposure energy is typically from about 10to 80 mJ/cm², dependent upon the exposure tool and the components of thephotosensitive composition.

Following exposure of the photoresist layer 104, a post-exposure bake(PEB) is performed. The PEB can be conducted, for example, on a hotplateor in an oven. Conditions for the PEB will depend, for example, on theparticular photoresist composition and layer thickness. The PEB istypically conducted at a temperature of from about 80 to 150° C., and atime of from about 30 to 90 seconds. Following post exposure bake, it isbelieved that the basic quencher diffuses into the surface region of thephotoresist layer 104 as shown by dashed lines 109. A latent image 116defined by the boundary (dashed line) between polarity-switched andunswitched regions (corresponding to exposed and unexposed regions,respectively) is formed in the photoresist as shown in FIG. 1B. Thediffused basic quencher in the photoresist is believed to preventpolarity switch in undesired dark regions of the photoresist layer,resulting in a latent image with vertical walls.

The overcoat layer 106 and exposed photoresist layer are next developedto remove unexposed regions of the photoresist layer 104, leavingexposed regions forming an open resist pattern 104′ with contact holepattern 120 having vertical sidewalls as shown in FIG. 1C. The developeris typically an organic developer, for example, a solvent chosen fromketones, esters, ethers, hydrocarbons, and mixtures thereof. Suitableketone solvents include, for example, acetone, 2-hexanone,5-methyl-2-hexanone, 2-heptanone, 4-heptanone, 1-octanone, 2-octanone,1-nonanone, 2-nonanone, diisobutyl ketone, cyclohexanone,methylcyclohexanone, phenylacetone, methyl ethyl ketone and methylisobutyl ketone. Suitable ester solvents include, for example, methylacetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate,propylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monobutyl ether acetate, diethyleneglycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutylacetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate,butyl formate, propyl formate, ethyl lactate, butyl lactate and propyllactate. Suitable ether solvents include, for example, dioxane,tetrahydrofuran and glycol ether solvents, for example, ethylene glycolmonomethyl ether, propylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monoethyl ether, diethylene glycolmonomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol. Suitable amide solvents include, for example,N-methyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide.Suitable hydrocarbon solvents include, for example, aromatic hydrocarbonsolvents such as toluene and xylene. In addition, mixtures of thesesolvents, or one or more of the listed solvents mixed with a solventother than those described above or mixed with water can be used. Othersuitable solvents include those used in the photoresist composition. Thedeveloper is preferably 2-heptanone or a butyl acetate such as n-butylacetate.

Mixtures of organic solvents can preferably be employed as a developer,for example, a mixture of a first and second organic solvent. The firstorganic solvent can be chosen from hydroxy alkyl esters such asmethyl-2-hydroxyisobutyrate and ethyl lactate; and linear or branched C₅to C₆ alkoxy alkyl acetates such as propylene glycol monomethyl etheracetate (PGMEA). Of the first organic solvents, 2-heptanone and5-methyl-2-hexanone are preferred. The second organic solvent can bechosen from linear or branched unsubstituted C₆ to C₈ alkyl esters suchas n-butyl acetate, n-pentyl acetate, n-butyl propionate, n-hexylacetate, n-butyl butyrate and isobutyl butyrate; and linear or branchedC₈ to C₉ ketones such as 4-octanone, 2,5-dimethyl-4-hexanone and2,6-dimethyl-4-heptanone. Of the second organic solvents, n-butylacetate, n-butyl propionate and 2,6-dimethyl-4-heptanone are preferred.Preferred combinations of the first and second organic solvent include2-heptanone/n-butyl propionate, cyclohexanone/n-butyl propionate,PGMEA/n-butyl propionate, 5-methyl-2-hexanone/n-butyl propionate,2-heptanone/2,6-dimethyl-4-heptanone and 2-heptanone/n-butyl acetate. Ofthese, 2-heptanone/n-butyl acetate and 2-heptanone/n-butyl propionateare particularly preferred.

The organic solvents are typically present in the developer in acombined amount of from 90 wt % to 100 wt %, more typically greater than95 wt %, greater than 98 wt %, greater than 99 wt % or 100 wt %, basedon the total weight of the developer.

The developer material may include optional additives, for example,surfactants such as described above with respect to the photoresist.Such optional additives typically will be present in minorconcentrations, for example, in amounts of from about 0.01 to 5 wt %based on the total weight of the developer.

The developer can be applied to the substrate by known techniques, forexample, by spin-coating or puddle-coating. The development time is fora period effective to remove the unexposed regions of the photoresist,with a time of from 5 to 30 seconds being typical. Development istypically conducted at room temperature. The development process can beconducted without use of a cleaning rinse following development. In thisregard, it has been found that the development process can result in aresidue-free wafer surface rendering such extra rinse step unnecessary.

The BARC layer, if present, is selectively etched using resist pattern104′ as an etch mask, exposing the underlying hardmask layer. Thehardmask layer is next selectively etched, again using the resistpattern 104′ as an etch mask, resulting in patterned BARC and hardmasklayers. Suitable etching techniques and chemistries for etching the BARClayer and hardmask layer are known in the art and will depend, forexample, on the particular materials of these layers. Dry-etchingprocesses such as reactive ion etching are typical. The resist pattern104′ and patterned BARC layer are next removed from the substrate usingknown techniques, for example, oxygen plasma ashing.

Using the hardmask pattern as an etch mask, the one or more layers 102are selectively etched. Suitable etching techniques and chemistries foretching the underlying layers 102 are known in the art, with dry-etchingprocesses such as reactive ion etching being typical. The patternedhardmask layer can next be removed from the substrate surface usingknown techniques, for example, a dry-etching process such as reactiveion etching. The resulting structure is a pattern of etched features. Inan alternative exemplary method, it may be desirable to pattern thelayers 102 directly using the resist pattern 104′ without the use of ahardmask layer. Whether direct patterning is employed will depend onfactors such as the materials involved, resist selectivity, resistpattern thickness and pattern dimensions.

The negative tone development methods of the invention are not limitedto the exemplary methods described above. For example, the photoresistovercoat compositions can be used in a negative tone development doubleexposure method for making contact holes. An exemplary such process is avariation of the technique described with reference to FIG. 1, but usingan additional exposure of the photoresist layer in a different patternthan the first exposure. In this process, the photoresist layer isexposed to actinic radiation through a photomask in a first exposurestep. The photomask includes a series of parallel lines forming theopaque regions of the mask. Following the first exposure, a secondexposure of the photoresist layer is conducted through a secondphotomask that includes a series of lines in a direction perpendicularto those of the first photomask. The resulting photoresist layerincludes unexposed regions, once-exposed regions and twice-exposedregions. Following the second exposure, the photoresist layer ispost-exposure baked and developed using a developer as described above.Unexposed regions corresponding to points of intersection of the linesof the two masks are removed, leaving behind the once- and twice-exposedregions of the resist. The resulting structure can next be patterned asdescribed above with reference to FIG. 1.

Further refined resolution for features such as contact holes and trenchpatterns can be achieved using an NTD overexposure process. In thisprocess, the photomask has large patterns relative to those to beprinted on the wafer. Exposure conditions are selected such that lightdiffuses beneath the edge of the photomask pattern causing the polarityswitch in the resist to extend beneath these edge regions.

EXAMPLES Synthesis of Photoresist Polymer (PP)

The structures of the monomers employed in the syntheses of photoresistpolymers are shown below along with their abbreviations:

Synthesis of Poly(ECPMA/MCPMA/MNLMA/HADA) (PP-1)

Monomers of ECPMA (5.092 g), MCPMA (10.967 g), MNLMA (15.661 g), andHADA (8.280 g) were dissolved in 60 g of PGMEA. The monomer solution wasdegassed by bubbling with nitrogen for 20 min PGMEA (27.335 g) wascharged into a 500 mL three-neck flask equipped with a condenser and amechanical stirrer and was degassed by bubbling with nitrogen for 20 minSubsequently the solvent in the reaction flask was brought to atemperature of 80° C. V601 (dimethyl-2,2-azodiisobutyrate) (0.858 g) wasdissolved in 8 g of PGMEA and the initiator solution was degassed bybubbling with nitrogen for 20 min. The initiator solution was added intothe reaction flask and then monomer solution was fed into the reactordropwise over the 3 hrs period under rigorous stirring and nitrogenenvironment. After monomer feeding was complete, the polymerizationmixture was left standing for an additional hour at 80° C. After a totalof 4 hrs of polymerization time (3 hrs of feeding and 1 hr ofpost-feeding stirring), the polymerization mixture was allowed to cooldown to room temperature. Precipitation was carried out in methyltert-butyl ether (MTBE) (1634 g). The power precipitated was collectedby filtration, air-dried overnight, re-dissolved in 120 g of THF, andre-precipitated into MTBE (1634 g). The final polymer was filtered,air-dried overnight and further dried under vacuum at 60° C. for 48 hrsto give Polymer PP-1 (Mw: 20,120 and PDI: 1.59).

Synthesis of Poly(MCPMA/NLM) (PP-2)

Monomers of MCPMA (17.234 g) and NLM (22.766 g) were dissolved in 60 gof PGMEA. The monomer solution was degassed by bubbling with nitrogenfor 20 min. PGMEA (31.938 g) was charged into a 500 mL three-neck flaskequipped with a condenser and a mechanical stirrer and was degassed bybubbling with nitrogen for 20 min. The solvent in the reaction flask wasbrought to a temperature of 80° C. V601 (dimethyl-2,2-azodiisobutyrate)(2.831 g) was dissolved in 8 g of PGMEA and the initiator solution wasdegassed by bubbling with nitrogen for 20 min. The initiator solutionwas added into the reaction flask and then monomer solution was fed intothe reactor dropwise over the 3 hrs period under rigorous stirring andnitrogen environment. After monomer feeding was complete, thepolymerization mixture was left standing for an additional hour at 80°C. After a total of 4 hrs of polymerization time (3 hrs of feeding and 1hr of post-feeding stirring), the polymerization mixture was allowed tocool down to room temperature. Precipitation was carried out in methyltert-butyl ether (MTBE) (1713 g). The power precipitated was collectedby filtration, air-dried overnight, re-dissolved in 120 g of THF, andre-precipitated into MTBE (1713 g). The final polymer was filtered,air-dried overnight and further dried under vacuum at 60° C. for 48 hrsto give Polymer PP-2 (Mw: 8,060 and PDI: 1.46)

Synthesis of Overcoat Polymers (OP)

The following monomers were employed in the syntheses of overcoatpolymers (OP) as described below:

Synthesis of Poly(iBMA/nBMA) (75/25) (OP-1)

30 g of iBMA and 10 g of nBMA monomers were dissolved in 60 g of PGMEA.The monomer solution was degassed by bubbling with nitrogen for 20 min.PGMEA (32.890 g) was charged into a 500 mL three-neck flask equippedwith a condenser and a mechanical stirrer and was degassed by bubblingwith nitrogen for 20 min. Subsequently the solvent in the reaction flaskwas brought to a temperature of 80° C. V601 (3.239 g) was dissolved in 8g of PGMEA and the initiator solution was degassed by bubbling withnitrogen for 20 min. The initiator solution was added into the reactionflask and then monomer solution was fed into the reactor dropwise overthe 3 hour period under rigorous stirring and nitrogen environment.After monomer feeding was complete, the polymerization mixture was leftstanding for an additional hour at 80° C. After a total of 4 hours ofpolymerization time (3 hours of feeding and 1 hour of post-feedingstirring), the polymerization mixture was allowed to cool down to roomtemperature. Precipitation was carried out in methanol/water (8/2)mixture (1730 g). The precipitated polymer was collected by filtration,air-dried overnight, re-dissolved in 120 g of THF, and re-precipitatedinto methanol/water (8/2) mixture (1730 g). The final polymer wasfiltered, air-dried overnight and further dried under vacuum at 25° C.for 48 hours to give 33.1 g of poly(iBMA/nBMA) (75/25) copolymer (OP-1)(Mw=9,203 and Mw/Mn=1.60).

Synthesis of Poly(iBMA/TBAEMA) (95/5) (OP-2)

37.433 g of iBMA and 2.567 g of TBAEMA monomers were dissolved in 60 gof PGMEA. The monomer solution was degassed by bubbling with nitrogenfor 20 min. PGMEA (28.311 g) was charged into a 500 mL three-neck flaskequipped with a condenser and a mechanical stirrer and was degassed bybubbling with nitrogen for 20 min Subsequently the solvent in thereaction flask was brought to a temperature of 80° C. V601 (1.276 g) wasdissolved in 8 g of PGMEA and the initiator solution was degassed bybubbling with nitrogen for 20 min. The initiator solution was added intothe reaction flask and then monomer solution was fed into the reactordropwise over the 3 hour period under rigorous stirring and nitrogenenvironment. After monomer feeding was complete, the polymerizationmixture was left standing for an additional hour at 80° C. After a totalof 4 hours of polymerization time (3 hours of feeding and 1 hour ofpost-feeding stirring), the polymerization mixture was allowed to cooldown to room temperature. Precipitation was carried out inmethanol/water (8/2) mixture (1651 g). The precipitated polymer wascollected by filtration, air-dried overnight, re-dissolved in 120 g ofTHF, and re-precipitated into methanol/water (8/2) mixture (1651 g). Thefinal polymer was filtered, air-dried overnight and further dried undervacuum at 25° C. for 48 hours to give 28.3 g of Poly(iBMA/TBAEMA) (95/5)copolymer (OP-2).

Additional Overcoat Polymers

Additional base-containing additive polymers were synthesized using theprocedure set forth above. The results including those for OP-1 and OP-2are summarized in Table 1.

TABLE 1 Polymer Monomer(s) Composition* Yield Mw Mw/Mn OP-1 iBMA/nBMA 75/25 77%  9,203 1.60 OP-2 iBMA/TBAEMA 95/5 71% NA NA OP-3 NPMA/TBAEMA95/5 75% 17,460 1.87 OP-4 NPMA/DEAEMA 95/5 80% 18,158 1.88 OP-5NPMA/TBAEMA 95/5 64% 56,698 1.31 OP-6 iBMA/DEAEMA 95/5 69% 14,414 2.19OP-7 NPMA/DMAEMA 95/5 76%  6,650 1.09 OP-8 NPMA/DMAPMA 95/5 77% NA NA*Molar feed ratio in the polymerization, NA = not available

Preparation of Photoresist Composition

1.294 g of PP-1 and 1.294 g of PP-2 were dissolved in 29.070 g of PGMEA,19.380 g of cyclohexanone, and 48.450 g of methyl-2-hydroxyisobutyrate.To this mixture was added 0.484 g of PAG A described below and 0.029 gof 1-(tert-butoxycarbonyl)-4-hydroxypiperidine. The resulting mixturewas rolled on a mechanical roller for three hours and then filteredthrough a Teflon filter having a 0.2 micron pore size.

Preparation of Resist Overcoat Composition (OC)

Resist overcoat compositions were prepared by dissolving overcoatpolymers in isobutyl isobutyrate (IBIB) using the components and amountsset forth in Table 2. The resulting mixtures were rolled on a mechanicalroller for three hours and then filtered through a Teflon filter havinga 0.2 micron pore size. The compositions were formulated based on targetthicknesses (after spin coating at −1500 rpm) corresponding to onequarter the wavelength of the incoming wave to reduce reflectance at theovercoat surface.

TABLE 2 Overcoat Target composition Polymer Solvent thickness, Å OC-1(Comp) OP-1 (1.500 g) IBIB (98.550 g) 290 OC-2 OP-2 (1.500 g) IBIB(98.550 g) 290 OC-3 OP-3 (1.500 g) IBIB (98.550 g) 290 OC-4 OP-4 (1.500g) IBIB (98.550 g) 290 OC-5 OP-5 (1.500 g) IBIB (98.550 g) 290Lithographic Process

Dry lithography was performed to examine the effect of base-boundovercoat polymers on 200 mm silicon wafers using a TEL CleanTrack ACT 8linked to an ASML/1100 scanner. Silicon wafers were spin-coated withAR™77 bottom-antireflective coating (BARC) material (Rohm and HaasElectronic Materials) and baked for 60 seconds at 205° C. to yield afilm thickness of 800 Å. Photoresist composition (PC) was coated on theBARC-coated wafers and soft-baked at 90° C. for 60 seconds on a TELCleanTrack ACT 8 coater/developer to provide a resist layer thickness of940 Å. Overcoat compositions as set forth in Table 2 were coated on topof the resist and soft-baked at 90° C. for 60 seconds on a TELCleanTrack ACT 8 coater/developer to provide an overcoat thickness of290 Å. The wafers were exposed using an annular illumination conditionwith 0.75 NA, 0.89 outer sigma and 0.64 inner sigma. The exposed waferswere post-exposure baked at 85° C. for 60 seconds and developed withn-butyl acetate (NBA) developer for 30 seconds on a TEL CleanTrack ACT 8coater/developer. CD was targeted at 100 nm dense contact holes with a200 nm pitch. As can be seen from Table 3, improved process window wasobserved with the use of base-bound polymer overcoats as compared withno overcoat composition (Comparative Example 1) and the comparativeovercoat composition (Comparative Example 2).

TABLE 3 Highest Dose without Overcoat Dose Latitude Missing ContactHoles Example Composition (nm/mJ) (mJ)/CD (nm) 1 (Comp) NA 7.8 25.0/63.62 (Comp) OC-1 6.4 28.0/60.8 3 OC-2 6.3 30.0/59.1 4 OC-3 5.2 30.0/57.5 5OC-4 6.7 30.0/55.8 6 OC-5 6.2 32.0/51.6

What is claimed is:
 1. A method of forming an electronic device,comprising in sequence: (a) providing a semiconductor substratecomprising one or more layers to be patterned; (b) forming a photoresistlayer over the one or more layers to be patterned, wherein thephotoresist layer is formed from a composition that comprises: a matrixpolymer comprising a unit having an acid labile group; a photoacidgenerator; and an organic solvent; (c) coating a photoresist overcoatcomposition over the photoresist layer, wherein the overcoat compositioncomprises a quenching polymer and an organic solvent, wherein thequenching polymer consists essentially of a first repeating unit havinga basic moiety effective to neutralize acid generated by the photoacidgenerator in a surface region of photoresist layer, and a secondrepeating unit formed from a monomer of the following general formula(I):

 wherein: R₁ is chosen from hydrogen and substituted or unsubstituted C1to C3 alkyl; R₂ is chosen from substituted and unsubstituted C1 to C15alkyl and is free of fluoroalkyl and fluoroalcohol; X is oxygen, sulfuror is represented by the formula NR₃, wherein R₃ is chosen from hydrogenand substituted and unsubstituted C1 to C10 alkyl; and Z is a singlebond or a spacer unit chosen from optionally substituted aliphatic andaromatic hydrocarbons, and combinations thereof, optionally with one ormore linking moiety chosen from —O—, —S—, —COO—and —CONR₄—wherein R₄ ischosen from hydrogen and substituted and unsubstituted C1 to C10 alkyland wherein the quenching polymer repeating units consist of the firstrepeating unit and the second repeating unit; (d) exposing thephotoresist layer to activating radiation; (e) heating the substrate ina post-exposure bake process; and (f) developing the exposed photoresistlayer with an organic solvent developer.
 2. The method of claim 1,wherein the first repeating unit having the basic moiety is formed froma monomer chosen from one or more of the following:


3. The method of claim 2, wherein the first repeating unit having thebasic moiety is formed from a monomer chosen from one or more of thefollowing:


4. The method of claim 1, wherein the first repeating unit having thebasic moiety is present in the polymer in an amount of from 0.1 to 30mol % based on the quenching polymer.
 5. The method of claim 1, whereinthe monomer of general formula (I) is a monomer of the following generalformula (II):

wherein R₅, R₆, and R₇ independently represent hydrogen or a C₁ to C₃alkyl.
 6. The method of claim 1, wherein Z is a single bond.
 7. Themethod of claim 1, wherein the quenching polymer is a random copolymer.8. The method of claim 1, wherein the quenching polymer is a blockcopolymer.
 9. The method of claim 1, wherein the quenching polymer is agradient copolymer.
 10. The method of claim 1, wherein the photoresistovercoat composition is free of acid generator compounds.
 11. A methodof forming an electronic device, comprising in sequence: (a) providing asemiconductor substrate comprising one or more layers to be patterned;(b) forming a photoresist layer over the one or more layers to bepatterned, wherein the photoresist layer is formed from a compositionthat comprises: a matrix polymer comprising a unit having an acid labilegroup; a photoacid generator; and an organic solvent; (c) coating aphotoresist overcoat composition over the photoresist layer, wherein theovercoat composition comprises a quenching polymer and an organicsolvent, wherein the quenching polymer consists essentially of: a firstrepeating unit having a basic moiety effective to neutralize acidgenerated by the photoacid generator in a surface region of photoresistlayer; and a second repeating unit formed from a monomer of thefollowing general formula (I):

 wherein: R₁ is chosen from hydrogen and substituted or unsubstituted C1to C3 alkyl; R₂ is chosen from C1 to C15 unsubstituted alkyl; X isoxygen, sulfur or is represented by the formula NR₃, wherein R₃ ischosen from hydrogen and substituted and unsubstituted C1 to C10 alkyl;and Z is a single bond or a spacer unit chosen from optionallysubstituted aliphatic and aromatic hydrocarbons, and combinationsthereof, optionally with one or more linking moiety chosen from —O—,—S—, —COO—and —CONR₄—wherein R₄ is chosen from hydrogen and substitutedand unsubstituted C1 to C10 alkyl; and all quenching polymer repeatingunits are chosen from the first repeating units having a basic moietyand the second repeating units formed from a monomer of general formula(I); (d) exposing the photoresist layer to activating radiation; (e)heating the substrate in a post-exposure bake process; (f) developingthe exposed photoresist layer with an organic solvent developer; and (g)etching the one or more layers using the developed photoresist layer asa mask.
 12. The method of claim 11, wherein the first repeating unithaving the basic moiety is formed from a monomer chosen from one or moreof the following:


13. The method of claim 11, wherein the first repeating unit having thebasic moiety is present in the polymer in an amount of from 0.1 to 30mol % based on the quenching polymer.
 14. The method of claim 11,wherein Z is a single bond.